( Reaffirmed 2003 ) IS : 9341 - 1979 Indian Standard SPECIFICATION SULPHAMIC Electroplating FOR ACID FOR ELECTROPLATING Chemicals Sectional Chairman Committee, CDC 43 ` Shubhodaya ' Mm hers SHRI S. K. BISWAS DR R. P. DANBAL SHRI R. D. KAWATRA DR S. KRISHNAMURTHY 38, XI Main Road, Malleswaram, Bangalore Representing Hindustan Copper Ltd, Calcutta Indian Telephone Industries Ltd, Bangalore Directorate General of Technical Development, New Delhi Phoenix Chemical Works Pvt Ltd, Bombay SHRI M. A. KOTIB~ASKAR SHRI M. A. CHUNEKAR ( Alternate ) Ministry of Defence ( DGI ) SnRI K. P. MAZUMDAR SHRI P. DATTA (Alternate ) Bharat Heavy Electricals Ltd, Bhopal DR V. S. MEHTA SHRI C. S. DIXIT ( Alternate ) Hindustan Zinc Ltd, Udaipur DR B. R. L. Row SARI G. L. JETWANI ( Alternate) SENIOR CI~EMIST AND METALLU- Diesel Locomotive Works (Ministry of Railways ), Varanasi RoIST AND CHEMIST ASSISTANT METALLU~GJST ( Alternate ) The Kesar Sugar Works Ltd, Bombay SHRI D. C. SIIAH Golden Chemicals Pvt Ltd, Bombay SHRI H. C. SHAH SBRI L. H. TIIAKKAR ( Alternate ) SHRI Y. hf. RAVAL (Alternate) Ronuk Industries Ltd, Bombay SHRI R. A. SHAH KUMARI MI~IDULA A. SHAII ( Alternate ) Institute Central Electra-Chemical Research Snc~ B. A. SliExOl ( CSIR ), Karaikudi DR N. V. PART~ASA~ADI~Y (Alternate ) D.evelopment Commissioner ( Small Seal e IndustSII~I V. TEIIAGARAJAN ries ), New Delhi T. I. Cycles of India, Madras Snnr R. VE~I~ATARAMAN Director General, IS1 (Ex-oficio Member) Dn G. M. SAXENA, Director (Chem ) Secretary SIIRI G. P. SARASWAT Deputy Director ( Chem ), IS1 @ INDIAN Copyright 1980 INSTITUTION STANDARDS This publication is protected under the Indian Copyrighf Act ( XIV of 1957) and reproduction in whole or in part by any means except with written permission of the publisher shall be deemed to be an infringement of copyright under the said Act. IS : 93411 1979 Indian Standard SPECIFICATION FOR SULPHAMIC ACID FOR ELECTROPLATING 0. FOREWORD 0.1 This Indian Standard was adopted by the Indian Standards Institution on 10 November 1979, after the draft finalized by the Electroplating Chemicals Sectional Committee had been approved by the Chemical Division Council. acid readily forms salts by reaction with oxides, hydroxides, Most metal sulphamates are solubIe and the carbonates or active metals. solutions conduct electricity weI1; this makes them useful as electroplating salts. Deposits from the sulphamates of cadmium, cobalt, copper, indium, lead, nickel, rhodium and silver, for example, are bright and dense. Plating baths of nickel sulphamate give good deposits for, electroforming. Baths of aluminium sulphamates are often preferred for the anodic oxidation They give abrasion and corrosionof aluminium and aluminium alloys. resistant finishes with good dye receptivity. 0-3 For standard sing the with IS rounded standard. the purpose of deciding whether a particular requirement of this is complied with, the final value, observed or calculated, expresresult of a test or analysis, shall be rounded off in accordance The number of significant places retained in the : T-1960*. off value should be the same as that of the specified value in this 0.2 Sulphamic 1. SCOPE I.1 This standard test for sulphamic prescribes requirements acid for electroplating. and methods of sampling and 2. REQUIREMENTS - Sulphamic acid shall be in the form of colourless or The white crystals free from dirt, foreign matter and visible impurities. material shall be freely soluble in water, but sparingly soluble in alcohol; and shall correspond essentially to the formula HO.SOsNH,. 2.1 Description *Rules for rounding off numerical values (revised). 2 IS : 9341 - 1959 2.2 The material shall also comply with the requirements Table 1 when tested in accordance with the methods Appendix A. Reference to the relevant clauses of Appendix co1 4 of the table. prescribed in prescribed in A is given in TABLE SL No. 1 REQUIREMENTiS FOR SULPIIAMIC FOR ELECTROPLATING RXQUIREMENT ACID METIIOD OF TEST ( REFTOCLNO. IN APPENDIX A ) (4) A-2 A-3 CIIARACTEXISTIC (2) i) ii) iii) iv) Mzat; i_n&uble in water, percent by Sulphaies ( as SO4 ), percent by mass, Max Heavy metals ( as Pb), percent by mass, Max Sulphamic acid ( as H0.S0gNH2), percent by mass, Min (3) 0.05 0.05 0.001 A-4 A-5 99.0 3. SAFETY PRECAUTIONS IN HANDLING SULPHAMIC ACID 3.1 Although brief contact of dry crystalline sulphamic acid with skin does not cause noticeable effect, precautions should be taken to avoid contact with eyes, skin or clothing and goggles and gloves should be worn when handling sulphamic acid, dry or in solution. In the event of contact, flush skin with water; flush eyes with plenty of water and get medical attention. 4. PACKING AND MARKING material shall be packed in high density polyethylene with polyethylene lining. with the following: 4.1 Packing - The woven bags provided 4.2 Marking a) Name - The bags shall be marked of the material and its net mass; and/or his recognized to enable trade-mark, if to be b) Name of the manufacturer any; and c) Lot number and date of manufacture traced from records. the material 3 IS : 9341- 1979 4.2.1 The bags may also be marked with the ISI Certification Mark. NOTE - The use of the IS1 Certification Mark is governed by the provisions of the Indian Standards Institution ( Certification Marks ) Act and the Rules and Regulations made thereunder. The IS1 Mark on products covered by an Indian Standard conveys the assurance that they have been produced to comply with the requirements of that standard under a well-defined system of inspection, testing and quality control which is devised and supervised by IS1 and operated by the producer. IS1 marked products are also continuously checked by IS1 for conformity to that standard as a further safeguard. Details of conditions under which a licence for the use of the IS1 Certification Mark may be granted to manufacturers or processors, may be obtained from the Indian Standards Institution. 5. SAMPLING 5.1 The method of preparing representative samples criteria for its conformity with this specification shall Appendix B. of the material and be as prescribed in APPENDIX ( Clause 2.2 ) METHODS A-l. A-l.1 QUALITY OF TEST A FOR SULPHAMIC ACID OF REAGENTS and distilled water impuri- Unless specified otherwise, pure chemicals ( see IS : 1070-1977* ) shall be used in tests. NOTE - ` Pure chemicals ' shall mean ties which affect the results of analysis. chemicals that do not contain A-2. DETE,RMINATION A-2.1 Procedure dried for two of water and sintered glass dry at 105 + A-2.2 OF MATTER INSOLUBLE IN WATER - Weigh accurately lO.Og of the material, previously hours over concentrated sulphuric acid. Dissolve in 75 ml Filter through a tared heat on a steam bath for 30 minutes. crucible ( G No. 4 ), wash the residue with hot water and 2°C to a constant mass. Calculation Matter insoluble in water, percent by mass where = 2 x 100 Ml = mass in g of the residue, and M = mass in g of the material taken for the test. *Specification for water for general laboratory `use ( secondrevision ). 4 IS : 9341 - lt979 A-3. DETERMINATION OF SULPHATES A-3.0 General - Turbidity produced by the addition of barium c!rloride solution to the solution containing the material is compared with that produced in the blank containing standard sulphate solution. A-3.1 Apparatus Kessler Cylinders Two of 50-ml capacity. A-3.1.1 A-3.2 Reagents Concentrated Hydrochloric Acid See IS : 265-1976*. by dissolving 12 g of A-3.2.1 A-3.2.2 Barium Chloride Solution barium chloride in 100 ml of water. Prepared A-3.2.3 Stsndard'Sulfihate Solution - Weigh accurately 0.181 5 g of potassium sulphate ( K2S04 ) and dissolve in water in a lOO-ml volumetric flask. One millilitre of this solution Make up the volume with water and mix. is equivalent to 0.1 mg of sulphate ( as SO1 ). I.00 g of the material, transfer to A-3.3 Procedure - Weigh accurately a 50-ml Nessler cylinder and add 2.5 ml of concentrated hydrochloric acid followed by 5 ml of barium chloride solution. Make up the volume with water and mix. Carry out a control test in another Kessler cylinder using 5 ml of standard sulphate solution and the same quantities of other reagents in the same total volume as with the material and compare the turbidity produced in the two cylinders against a black background. A-3.3.1 The material shall be taken as having not exceeded the limit prescribed for sulphates in Table 1 if turbidity produced with the material is not greater than that produced in the control test. A-4. DETERMINATION OF HEAVY METALS A-4.0 General - The colour produced by the addition of hydrogen sulphide solution to the solution containing the material is compared with that produced in the blank containing standard lead solution. A-4.1 Apparatus .Nessler Cylinders Same as prescribed in A-3.1.1. A-4.1.1 A-4.2 Reagents Ammonium Hydroxide relative ( secondrezhion A-4.2.1 density ). 0.9. *Specification for hydrochloric acid 5 IS:9341-1979 accurately 0.160 g of lead A-4.2.2 Standard Lead Solution - Weigh nitrate [ Pb ( NOs ) 2 ] and dissolve in 50 ml of water, containing 1 ml of concentrated nitric acid in a lOO-ml volumetric flask, make up to the mark with water and mix. Dilute 10 ml of this solution to 100 ml with water. One millilitre of this diluted solution is equivalent to 0.01 mg of lead (asPb). A-4.2.3 Dilute Acetic Acid approximately freshly 1 N. prepared saturated aqueous A-4.2.4 Hydrogen Suljhide Solution solution of hydrogen sulphide. A-4.3 Procedure - Weigh accurately I.00 g and 3.00 g respectively of the material into two Nessler cylinders marked ( A ) and ( B ) and To the solution contained in (A ) add 2 ml dissolve in 30 ml of water. of the standard lead solution followed by 2 ml of dilute acetic acid. Dilute up to the mark with water and mix. Similarly, to the soluticn contained in ( B ) add 2 ml of dilute acetic acid. Dilute to the mark with water and mix. Then add to each Nessler cyhnder 10 ml of hydrogen sulphide solution and mix. A-4.3.1 The material shall be taken as having not exceeded the limit prescribed for heavy metals in Table 1 if the colour produced in Nessler cylinder ( B ) is not darker than that produced in ( A ). A-5. DETERMINATION OF SULPHAMIC ACID A-5.0 General - Sulphamid acid content is determined volumetrically by addition of sodium nitrite and titration of excess by standard potassium permanganate solution. A-5.1 Reagents Dilute Sulphuric Acid Standard 10 percent ( v/v). approximately Solution 0.1 N. 0.1 N. A-5.1.1 A-5.1.2 A-5.1.3 Sodium .Nitrite Solution Permanganate Standard Potassium approximately A-5.2 Procedure - Weigh accurately about 0.5 g of the material, and dissolve in 100 ml of water. Transfer to a 500-ml volumetric flask and Pipette 100 ml of this solution into a dilute up to the mark with water. 400 ml beaker; add 20 ml of dilute sulphuric acid and 25 ml of standard Swirl gently for one minute and add 10 ml of sodium nitrite solution. Heat the solution to about standard potassium permanganate solution. 70°C. The permanganate colour should persist. Otherwise add another Back titrate excess 10 ml of permanganate solution immediately and stir. 6 iS : 9341 - 1979 potassium permanganate with standard solution becomes just colourless. NOTE - Standardize ganate solution. A-5.3 sodium nitrite sodium nitrite solution till the solution against 0.1 N potassium perman- Calculation Sulphamic where V = total volume in ml of standard consumed in the test ( A-5.2), of standard sodium potassium potassium in the sodium nitrite solution acid content, percent by mass = 4.95 ( VNM v, N, ) N = normality nitrite solution, solution solution, for the V, = volume in ml of standard added ( A-5.2 ), JQ = normality and test. of standard permanganate permanganate aliquot taken M = mass in g of the material APPENDIX ( Clause 5.1 ) SAMPLING R-l. E-l.1 GENERAL OF SULPHAMIC REQUIREMENTS B ACID FOR ELECTROPLATING FOR SAMPLING and handling clean, test samples, the In drawing, preparing, storing following precautions shall be observed. B-l.2 The containers. samples shall be placed in suitable, dry and air-tight B-l.3 While handling the test samples, precautions shall be taken to avoid contact with eyes, skin or clothing and goggIes and gloves shall be worn. B-l.4 The sampled material not be exposed to damp air. shall be kept in a protected place and shall B-l.5 Each sample cbntainer shall be sealed air-tight full details of sampling, such as the date of sampling, facture, ttle lot number and name of the manufacturer. 7 and marked with the year of manu- 16: 9341 - 1939 `B-2. SCALE OF SAMPLING B-2.1 All the bags in a single a single batch of manufacture consignment shall constitute of the material a lot. drawn from B-2.2 For ascertaining conformity of the material in the lot to the requirements of the specification: samples shall be tested from each lot separately. B-2.3 The number of bags to be chosen the size of the lot and shall be according TABLE LOT SIZE from the lot shall to Table 2. depend upon 2 SCALE OF SAMPLING NUYBEROFBAGSTOBE SELECTED N (1) up to 25 26 )) 50 51 ), 100 101 )) 300 301 and above cb 3 4 5 6 7 B-2.3.1 The bags to be selected for this purpose shall be chosen In order to ensure randomness of selection, at random from the lot. reference may be made to IS : 4905-1968*, In case this standard is not readily available, the following procedure may be adopted: ` Starting from any bag in the Iot count them in one order as 1, 2, 3,...etc, up to t and so on where r is the integral part of N/n. Every rth bag thus counted shall be withdrawn till the requisite number of bags is obtained. B-3. TEST SAMPLES AND REFEREE SAMPLE B-3.1 From each of the bags selected according to B-2.3 draw small quantity of material from different parts of the bag with the help of a suitable sampling implement. The quantity of the material drawn from each bag shall be thoroughly mixed and shall be sufficient to make triplicate determinations for all requirements given in Table 1. B-3.2 Out of the portions of the material from all the bags selected according to B-2.3, approximately equal quantity of-the material shall be taken and mixed together so as to form a composite sample of quantity *Methods for random sampling. 8 IS : 9341 - 1979 sufficient to carry out triplicate determinations to be tested on the composite sample. for all the characteristics B-3.2.1 The composite sample shall be divided into three equal parts, one for the purchaser: another for the supplier and the third to be used as a referee sample. B-3.3 The remaining parts of the material from each selected bag shall be divided into three equal parts, each forming an individual sample. One set of individual samples representing each selected bag shall be marked for the purchaser, another for the supplier and the third to be used as a referee sample. B-3.4 All the individual and the composite samples shall be immediately transferred to separate sample containers and labelled with full identification particulars, B-3.5 The referee sample consisting of a composite and a set of individual samples shall bear the seals of both the purchaser and the supplier. These shall be kept at a place agreed to between the purchaser and the supplier, to be used in case of a dispute between the two. B-4. NUMBER OF TESTS B-4.1 Test for determining sulphamic acid content shall be conducted on each of the individual samples. B-4.2 Tests for the remaining requirements, be conducted on the composite sample. B-5. CRITERIA FOR CONFORMITY prescribed in Table 1, shall B-5.1 Test on Individual Samples - From the test results for sulphamic acid content, the mean ( X) and the range ( ti ) of test results shall be calculated (range being defined as the difference between the maximum and the minimum values of test results ). The lot shall be declared to have satisfied this requirement if the value of the expression (X - 0.6 R ) is greater than or equal to 99.0. B-5.2 Tests on the Composite Sample - The lot shall be considered to have passed in respect of the characteristics tested on the composite sample ( seeB-4.2 ) if all the test results on the composite sample satisfy the corresponding requirements given in Table 1, B-5.3 The lot shall be declared as conforming specification if B-5.1 and B-5.2 are satisfied. to the requirements of this INDIAN ON STANDARDS ELECTROPLATING CHEMICALS IS: 330-1968 1809-1979 1880-1977 2214-1977 3026-1968 4846-1968 4847-1978 5003-1968 5761-1970 6267-1971 6358-1971 6588-1972 7038-1973 7067-1973 8590-1977 9341-1979 9342-1979 Chromium Nickel Silver Sodium trioxide (jrst revision ) ( second revision ) (first revision) (Jirst revision ) reagent salt ) salts for electroplating nitrate, Zinc oxide and zinc salts for electroplating pure and analytical tartrate Tin salts for electroplating potassium (first revision ) ( Rochelle Copper salts for electroplating Cadmium oxide for electroplating Gold cyanide Silver cyanide Potassium Gold chloride Chloroplatinic Fluoboric Indium Sodium Sulphamic sulphate (first revision ) cyanide cyanide for electroplating for electroplating and gold potassium and silver potassium ( chloroauric acid ( platinic acid ) and sodium cyanides for electroplating chloride ) for electroplating acid and metal fluoborates for electroplating for electroless plating acid for electroplating hypophosphite